BR112012004223B1 - mixtures of isomeric nonyl esters, processes for the preparation of mixtures of isomeric nonyl esters, compositions and uses of isomeric nonyl esters and the composition - Google Patents

Abstract

NONILA ESTER MIXTURES, PROCESS FOR THE PREPARATION OF NONILA ESTER MIXTURES, COMPOSITIONS AND USE OF NONILA ESTERS AND COMPOSITION USES. The present invention relates to the mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (I), methods for said production of mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (I), compositions containing mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (I), uses of mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (I) as plasticizers, and uses of the previously mentioned compositions containing a mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula (I).

Description

FIELD OF THE INVENTION

[001] The present invention relates to a mixture of esters of 2,5-furanedicarboxylic acid (FDCA) with C9 isomeric alcohols, more particularly mixtures of straight and branched nonanools. The present invention also relates to a process for the preparation of such esters and mixtures and the use of them as plasticizers for polymers, such as polyvinyl chloride, for example.

BACKGROUND OF THE INVENTION

[002] Polyvinyl chloride (PVC) is among the most economically important polymers. It finds diverse applications in non-plasticized PVC and plasticized PVC.

[003] To produce a plasticized PVC, PVC is mixed with plasticizers, for which, in the vast majority of cases, phthalic acid esters are used, more particularly, di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP). As a result of the legal regulations that already exist, and possible future regulations regarding the restricted use of phthalates, there is a need to find new esters suitable as plasticizers for PVC and other polymers, where, preferably, the same alcohols as before can be used . In view of the limited availability of fossil raw materials, in particular, such esters should have good market opportunities in the future, where at least the acid component is based on natural sources, such as sugars, fats or oils.

[004] In the publication “Top Value Added Chemicals from Biomass”, by T. Werpy and G. Petersen (US Dept. Of Energy (DOE); 08/2004), 2,5-furanedicarboxylic acid (FDCA) is considered a of the most promising sugar-based platform chemicals. Due to its structural similarity to terephthalic acid, the last few years have been accompanied by the publication of numerous articles on the use of 2,5-furanedicarboxylic acid or various derivatives, mainly in polymers. The main application in most cases has been the partial or complete replacement of terephthalic acid or its derivatives in polymers. A very comprehensive review of FDCA, its applications and its possibilities for synthesis is found in the publication on the Internet by Jaroslaw Lewkowski, ARKIVOC 2001 (i), pages 1754, ISSN 1424-6376, with the title “Synthesis, Chemistry and Applications of 5- hydroxymethylfurfural and its derivatives ”. Common to most of these syntheses is an acid-catalyzed reaction of carbohydrates, especially glucose or fructose, preferably fructose, to provide 5-hydroxymethylfurfural (5-HMF), which can be isolated from the reaction medium by processing operations, such as a two-phase regime, for example. The corresponding results have been described, for example, by Roman-Leshkov et al., In Science 2006, 312, pages 1933 to 1937, and by Zhang in Angewandte Chemie 2008, 120, pages 9485 to 9488.

[005] In another step, 5-HMF can then be oxidized to FDCA, as quoted by Christensen in ChemSusChem 2007, 1, pgs. 75-78, for example.

[006] In addition, the preparation of some esters of FDCA by direct synthesis from muscic acid is also described (Tagouchi in Chemistry Letter vol. 37, No. 1 (2008)) and the corresponding alcohols.

[007] The use of 2,5-furanedicarboxylic acid esters as plasticizers for plastics, in particular PVC, PVB, PLA, PHB or PAMA, has not been frequently described so far. The most extensive review, in this context, is found in the publication by R.D. Sanderson et al., In Journal of Appl. Pol. Sci. 1994, vol. 53, p. 1785-1793. The corresponding esters based on n-butanol, n-hexanol, 2-octanol and 2-ethylexanol are explicitly described. Investigations on the interaction of esters with PVC show that they could be used as plasticizers for PVC. However, these conclusions were drawn only from measures of DMTA. Performance investigations, which are important and most significant to the processor, have not been carried out. There is also no reference, for example, to the fact that the FDCA 2-ethylhexyl ester tends to crystallize at relatively low temperatures, as can be demonstrated by DSC measurements (maximum melting point at 12 ° C with starts at - 2.7 ° C). Therefore, for many processors, this ester will have only limited utility, since at low temperatures there is no guarantee of pumping capacity.

[008] An additional factor is the classification of 2-ethylexanol as a dangerous substance, which imposes limits on its usefulness, especially in sectors that come into contact with the skin and / or in contact with food.

[009] Starting from the state of the art, therefore, the object was to provide esters based on 2,5-furanedicarboxylic acid that can be used as plasticizers for plastics, such as PVC, PVB, PLA, PHB or PAMA, for example, with which the aforementioned problem does not occur or occurs only in a markedly attenuated manner, and which have the technical potential to replace the current standard petrochemical plasticizers.

DESCRIPTION OF THE INVENTION

[010] It has been found that mixtures of isomeric nonyl esters of 2,5-furanedicarboxylic acid (Formula I) can be used as plasticizers for plastics, more particularly in PVC, PVB, PLA, PHB and PAMA, in which they exhibit advantageous properties in relation to the FDCA esters known in the literature. In addition, in relation to the corresponding esters of phthalic acid, these esters also exhibit performance advantages.

[011] The present invention provides mixtures of isomeric nonyl esters of 2,5-furanedicarboxylic acid of formula I. Still provided by the present invention are compositions comprising mixtures of isomeric nonyl esters of 2,5-furanedicarboxylic acid of Formula I .

[012] With regard to the raw material base, the particular feature of the present invention lies in the optional use of renewable raw materials for the preparation of the furanodicarboxylic esters of the present invention. Renewable raw materials are understood in the sense of the present invention, in contrast to petrochemical raw materials that are based on fossil resources, such as oil or coal, for example, as the raw materials that form or are produced based on biomass. The terms "biomass", "biological basis" or "based on and / or produced from renewable raw materials" cover all materials of biological origin, which comes from the so-called "short-term carbon cycle" and therefore , are not part of geological formations or fossil strata. The identification and quantification of renewable raw materials is carried out according to the ASTM Method D6866 standard. A characteristic of renewable raw materials, among others, is their fraction of the 14C carbon isotope, in contrast to petrochemical raw materials.

[013] A certain economic and at the same time environmental advantage of the present invention lies in the simultaneous use of renewable and petrochemical raw materials for the preparation of the furanodicarboxylic esters of the present invention, this not only allows for particularly cheap production and wide applicability, but also leads to particularly sustainable products.

[014] The present invention further provides for the use of these mixtures in paints, dyes or varnishes, in plastisols, adhesives or adhesive components, in sealants, as plasticizers in plastics or plastic components, as solvents, as a lubricating oil component and as a metal processing aid, and also provides a PVC composition or a plastisol comprising PVC and from 5 to 250 parts by weight of the mixture of the present invention per 100 parts by weight of PVC.

[015] The present invention also provides a process for the preparation of mixtures of isomeric non-ester esters of 2,5-furanedicarboxylic acid, characterized by the fact that 2,5-furanedicarboxylic acid is esterified with a mixture of isomeric nononals, called below as isononanol, optionally in the presence of a catalyst, or dimethyl 2,5-furanedicarboxylate is transesterified with isononanol, with methanol release, optionally using a catalyst, to check the mixture of isomeric nonyl esters of acid 2.5 - furanodicarboxylic.

[016] For the preparation of a mixture of isomeric nonyl esters, it is additionally possible to start from muscic acid, as well, which, in the presence of isomeric nonanols and, preferably, with acid catalysis, is simultaneously - in a reaction of single step - cyclized and reacted to provide the corresponding furanodicarboxylic ester.

[017] In relation to the prior art furanodicarboxylic esters, but also in relation to the present di (isononyl) phthalate (DINP) plasticizer, the FDCA isomeric nonyl ester mixtures of the present invention exhibit significantly better properties in the context of their use as plasticizers in plastics, especially PVC.

[018] In relation to esters of the prior art FDCA based on 2-ethylexanol, the diisononyl esters of the present invention have a lower volatility of the film and, also, in plastisols, a smaller increase in viscosity over time and, therefore, better aging stability. In addition, the isononanol ester mixture based on the present invention, in contrast to the di-2-ethylhexyl ester, shows no tendency to crystallize in the -20 ° C range, but instead presents a transition point glassy of only about -80 °. Interestingly, in terms of properties that are central to the user, the diisononyl esters of the present invention also exhibit properties that are better than those of the corresponding phthalate (diisononyl phthalate, DINP), such as, for example, faster gelling and better plasticizing effect. For the processor, this means either a lower processing temperature or, for a given processing temperature, a higher production rate per unit time, in combination with the present effect in which less plasticizer is required for the same degree of plasticity / flexibility as is the case with the corresponding phthalate.

[019] The composition of the 2,5-furanedicarboxylic acid isomeric nonyl ester mixtures of the present invention is preferably such that the mixture comprises at least two different esters which differ in the constitution of the C9isomeric radicals, with none of the C9 radicals present in the mixture with a fraction greater than 90 mol%.

[020] The blend of the present invention can consist exclusively of mixtures of Formula I esters or can also comprise at least one polymer and / or at least one plasticizer that is not a Formula I diester. Plasticizers can be selected, for example , from citric acid trialkylesters, citric acid acylated trialkylesters, glycerol esters, glycol dibenzoates, alkyl benzoates, dialkyl adipates, trialkyl trimellitates, dialkyl terephthalates, dialkyl phthalates or dialkyl acid esters -, 1,3-, or 1,4-cyclohexanedicarboxylic, alkyl radicals containing 4 to 13, preferably 5, 6, 7, 8, 9, 10, 11 or 13 carbon atoms. Plasticizers can also be dianhydroxytol esters, preferably isosorbide diesters of carboxylic acids, such as n- or isobutyric acid, valeric acid or 2-ethylexanoic acid or isononanoic acid, for example.

[021] The polymers that may be present in the mixture of the present invention are, for example, polyvinyl chloride (PVC), polyvinyl butyral (PVB), polylactic acid (PLA), polyhydroxybutyral (PHB) and polyalkyl methacrylates (PAMA). With particular preference, the polymer is polyvinyl chloride (PVC).

[022] In preferred mixtures comprising Formula I diesters and polymers, the weight ratio of the polymer / polymers to diester / Formula I diesters is preferably from 30: 1 to 1: 2.5 and from most preferred, from 20: 1 to 1: 2.

[023] In preferred mixtures comprising Formula I diesters and plasticizers that are not a Formula I diester, the molar ratio of plasticizers, more particularly of alkyl benzoates, dialkyl adipates, glycerol esters, citric acid trialkyl esters , acylated citric acid trialkyl esters, trialkyl trimellites, dibenzoates glycol, dialkyl terephthalates, dialkyl phthalates, dialkoyl isosorbide esters and / or dialkyl esters of 1,2-, 1,3- or 1,4-cyclo-acid hexanedicarboxylic, for the diester / diesters of Formula I is preferably from 1:15 to 15: 1, more preferably from 1: 6 to 6: 1.

[024] The Formula I diester mixtures of the present invention, and the Formula I diesters themselves, can be prepared in a variety of ways. Preferably, mixtures of Formula I diesters and / or Formula I diesters are prepared by the process described below.

[025] The process of the present invention for the preparation of isomeric nonyl esters of 2,5-furanedicarboxylic acid is distinguished by the fact that 2,5-furanedicarboxylic acid or a relatively short-chain dialkyl ester of this compound, especially the dimethyl ester, is reacted with a mixture of isomeric nonanols, with a catalyst being used optionally. In addition, the 2,5-furanedicarbonyl dichloride that can be obtained by reacting the FDCA with chlorinating agents, such as thionyl chloride, for example, can be used as a starting material for the preparation of diisononyl esters. Suitable conditions for the FDCA reaction to supply the diisononyl ester through dichloride as an intermediate are found in the examples.

[026] It is preferred to use a mixture of isomeric nonanols comprising at least two nonanols of empirical formula C8H17CH2OH with different constitutional formulas, with none of the nonyl alcohols present in the mixture containing a fraction, preferably greater than 90 mol%.

[027] Preferably, mixtures of isomeric nonanols of empirical formula C9H19OH, more particularly of formula C8H17CH2OH, which are used in the process of the present invention contain less than 10 mol%, preferably less than 5 mol%, of greater preferably less than 1 mol%, and most preferably 0 to 0.5 mol%, preferably less than 0.1 mol%, more preferably 0.0001 to 0.1 mol%, and more preferably less than 0.05 mol%, more preferably 0.01 to 0.05 mol%, 3,5,5-trimethylexanol or other alcohol non-substituted nonila having the empirical formula C8H17CH2OH, especially those with quaternary C atoms. The presence of these alcohols impairs the performance properties and reduces the rate of biodegradation of the molecule.

[028] It may also be advantageous if the isononanols of the empirical formula C9H19OH, more particularly of the formula C8H17CH2OH, which are used for the preparation of the diesters of Formula I present in the mixture of the present invention, contain from 1% to 85%, of preferably from 1% to 50%, more preferably from 2% to 20%, of n-nonanol.

[029] The isomer distributions of isomeric alcohols in the mixtures can be determined using the usual measurement methods known to those skilled in the art, such as NMR spectroscopy, GC or GC / MS spectroscopy, preferably following conversion to esters of silyl or methyl.

SYNTHESIS OF NONILA ISOMERIC ALCOHOLS

[030] In principle, all technical mixtures of nonanols having the empirical formula C9H19OH, more particularly those having the formula C8H17CH2OH, which have at least two different types of constitutional isomers, can be used. It is preferred to use mixtures of isomeric nonanols with the formula C8H17CH2OH which, in terms of the fraction of the different isomers and / or the amount of C9 alcohols with quaternary C atoms, are within the ranges indicated above.

[031] Mixtures of isomeric nonanols with the empirical formula C9H19OH, more particularly, the formula C8H17CH2OH (referred to below isononanols), which are used in the process of the present invention, can be prepared, for example, by hydroformylation of octenes, which in turn instead, they can be produced in a variety of ways, and subsequent hydrogenation.

[032] As raw material for the preparation of octenes, it is possible to use technical C4 streams that initially contain all isomeric C4 olefins, as well as saturated butanes and possibly impurities such as C3 and C5 olefins and acetylenic compounds. The oligomerization of olefins present in C4 streams produces predominantly isomeric mixtures of octene, together with higher oligomers, such as mixtures of C12 and C16 olefins. These octene mixtures, possibly after removal by distillation of the C12 and C16 olefins, can be hydroformylated to the corresponding aldehydes and subsequently hydrogenated in alcohol. The composition, that is, the distribution of the isomer, of the mixtures of technical nonanol is dependent on the starting material and substantially dependent on the oligomerization and hydroformylation processes.

[033] The mixtures of octene that can be used include, for example, those obtained by the process known as the Polygas process, in which mixtures of C3 / C4 are oligomerized on a solid acid catalyst, preferably a phosphoric acid catalyst solid (SPA process). This process is described in documents, including US 6,284,938, US 6,080,903, US 6,072,093, US 6,025,533, US 5,990,367, US 5,895,830, US 5,856,604, US 5,847,252, US 5,081 .086. If mixtures of olefins obtained exclusively in this way are hydroformylated, the product generally also includes octane and decanal fractions, so that the average chain length at present can deviate from 9 carbon atoms. After hydrogenation, therefore, a mixture is obtained, which contains isomeric nonanols and which may also contain isomeric octanols or decanols. In addition, ethylene oligomerization octenes can also be used to advantage.

[034] The particularly preferred mixtures of isomeric nonanols that can be used in the process of the present invention are those that are viable by hydroformylation of the isomeric octenes and, subsequently, hydrogenation of the resulting aldehydes, with the mixture of isomeric octenes being obtained by contacting a hydrocarbon mixture comprising butenes, with a fraction of isobutene, preferably less than 20% by weight, more preferably less than 10% by weight, more preferably still less than 5% by weight, more preferably , still, less than 3% by mass, most preferably still less than 1% by mass, more preferably still between 0.01% and 1% by mass, and most preferably still between 0 , 05% and 0.5% by mass, based on butenes, with an oligomerization catalyst, preferably a catalyst containing nickel oxide. The preparation of isomeric octenes by oligomerization of substantially linear butenes on nickel-supported catalysts is known, for example, in the form of an OCTOL process, which is described in EP 0.395.857 or EP 1.029.839, for example . In variants of the OTOL process, catalysts containing Ti or Zr, for example, are used. Such alternative variants and particularly catalysts are described in EP 1,171,413, for example. As already described above, the resulting octenes can be separated from the upper olefins - that is, from the C12, C16, C20, olefins, etc. - by means of distillation, for example.

[035] Octenes or mixtures of isomeric octenes prepared as described above, for example, are subsequently pursued for hydroformylation. Hydroformylation can occur in the presence of modified or unmodified cobalt or rhodium catalysts. Hydroformylation preferably takes place in the presence of unmodified cobalt compounds. Suitable hydroformylation processes are known from EP 0.850.905 and EP 1,172,349, for example. In general, a mixture is obtained in this way by being constituted by substantially isomeric non-channels, optionally octenes that have not yet reacted, and also the corresponding mixtures of isomeric and octanes formed by hydrogenation (following the reaction).

[036] Hydroformylation can also occur in the presence of rhodium catalysts. Hydroformylation processes of this type are common knowledge, for example, from the documents EP 0.213.639, EP 1.201.675, WO 03/16320, WO 03/16321, WO 2005/090276, and the documents cited in the present . Special processes for hydroformylation, which are also suitable for the preparation of mixtures of isomeric nonanols which can be used in the process of the present invention, are described in WO 2004/020380 or DE 10.327.435, for example. The processes described herein are carried out in the presence of cyclic carbonic esters.

[037] It may also be advantageous to fractionate the mixture of isomeric octenes to start, as described in EP 1,172,349, before proceeding to hydroformylation. In this way it is possible to obtain fractions of octene which are especially suitable for the preparation of mixtures of isomeric nonanols which can be used in the process of the present invention. From the fractions it is then possible, in a relatively simple way, by mixing appropriate fractions, to obtain a mixture of isomeric octenes which is suitable for the preparation of isomeric nonanole mixtures for use in the process of the present invention.

[038] Hydroformylation of octene mixtures can be carried out in one or more stages, optionally with removal of unreacted octenes after each stage. The reaction mixture obtained from hydroformylation can be optionally - and preferably is - fractionated, thus concentrating the fraction of nonanal destined for hydrogenation. In general, however, the hydroformylation product will be directly released from the catalyst and then fed into the hydrogenation. In general, hydrogenation occurs above heterogeneous catalysts, at elevated temperatures and pressures, in a conventional liquid or gas phase regime, as described in WO 2009/027135, for example.

[039] Suitable isononanol mixtures for the purposes of the present invention are also specified in EP 1,171,413, for example. FURANODICARBOXYLIC ACID

[040] 2,5-furanedicarboxylic acid (FDCA, CAS: 3238-40-2), a white solid that has a melting point above (>) 300 ° C, is not available, on an industrial scale, until now. , but it can be prepared according to the literature or purchased commercially. Conversion to dichloride, which may be desired or preferred is described in detail in the examples. STERIFICATION

[041] For the preparation of the esters of the present invention, furanodicarboxylic acid or a reactive derivative, such as the corresponding dichloride, for example (see examples), is reacted with a mixture of isomeric nonanols. The esterification takes place, preferably, from furanodicarboxylic acid and isononanol, with the aid of a catalyst.

[042] The esterification of furanodicarboxylic acid with an isononanol mixture to provide the corresponding esters can be carried out autocatalytically or catalytically, with Br0nsted or Lewis acids, for example. Regardless of the type of catalysis selected, there is always a temperature-dependent balance developed between the reagents (acid and alcohol) and the products (ester and water). In order to shift the balance in favor of the ester, an anterior azeotrope can be used to help remove the reaction water from the batch. Since the alcohol mixtures used for the esterification boil at a lower temperature than furanodicarboxylic acid, its reactive derivatives, and its esters, and exhibit a water miscibility gap, they are often used as an anterior azeotrope and can be recycled to the process after removing the water.

[043] The alcohol used to form the ester or isomeric mixture of nonanol that serves simultaneously as the anterior azeotrope is used in excess, preferably from 5% to 50% by weight, more preferably from 10% to 30% in bulk. mass of the amount needed to form the ester.

[044] As esterification catalysts it is possible to use acids, such as sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, for example, or metals or compounds thereof. Suitable examples include tin, titanium, zirconium, which are used as finely divided metals or usefully in the form of their salts, oxides or soluble organic compounds. In contrast to protic acids, metal catalysts are high temperature catalysts, which often reach their full activity only at temperatures above 180 ° C. Here, however, it must be borne in mind that furanodicarboxylic acid tends to supply CO2 at temperatures above 190 ° C, and then monocarboxylic acid is formed from then on, and can no longer react to supply the target product. However, metal catalysts are preferably used, since compared to proton catalysis, they form less by-products from the alcohol used, such as olefins, for example. Exemplary representatives of metal catalysts are tin powder, tin (II) oxide, tin (II) oxalate, titanic esters, such as tetraisopropyl orthotitanate or tetrabutyl orthotitanate, and zirconium esters, such as tetrabutyl zirconate .

[045] The concentration of catalyst is dependent on the type of catalyst. In the case of the titanium compounds preferably used, the concentration is from 0.005% to 2.0% by mass, based on the reaction mixture, more preferably, from 0.01% to 0.5%, by mass, of greater preferably from 0.01% to 0.1% by mass.

[046] The reaction temperatures when using titanium catalysts are between 160 ° C and 270 ° C, preferably between 160 and 200 ° C. The optimum temperatures are dependent on the reagents, the progress of the reaction and the concentration of catalyst . They can be easily determined by experiments for each individual case. Higher temperatures increase reaction rates and promote secondary reactions, such as the elimination of water from alcohols or the formation of colored by-products, for example. A beneficial fact regarding the removal of water from the reaction is that the alcohol can be removed by distillation from the reaction mixture. The desired temperature or the desired temperature range can be caused by pressure in the reaction vessel. Therefore, in the case of low boiling alcohols, the reaction is carried out at superatmospheric pressure, and at reduced pressure in the case of higher boiling alcohols. In the case of the reaction of FDCA with a mixture of isomeric nonanols, for example, the operation takes place in a temperature range of 160 ° C to 190 ° C in the pressure range of 0.1 MPa to 0.001 MPa.

[047] The amount of liquid to be recycled for the reaction can consist of all or part of the alcohol obtained when working the azeotropic distillate. It is also possible to carry out the purification at a later time and replace some or all of the amount of liquid removed with fresh alcohol, that is, from an alcohol prepared in a reservoir vessel.

[048] Mixtures of crude ester, which in addition to the ester or esters include alcohol, the catalyst or its subsequent products and, optionally, by-products, are purified by conventional methods. This purification includes the following steps: removal of excess alcohol and, when present, low boiling point products; neutralization of the acids present; optionally a steam distillation; converting the catalyst to a residue that is easily filterable; removal of solids; and, optionally, drying. The sequence of these steps may differ according to the purification procedure employed.

[049] The mixture of the diisononyl esters can optionally be separated from the reaction mixture by distillation, optionally after neutralization of the batch. T RANSESTERIFICATION

[050] The diisononyl esters of the present invention can alternatively be obtained by transesterification of a 2,5-furanedicarboxylic diester with a mixture of isononanol. The reagents used are 2,5-furanedicarboxylic diesters whose alkyl radicals attached to the O atom of the ester group contain 1 to 8 C atoms. These radicals can be aliphatic, straight chain or branched, alicyclic or aromatic. One or more methylene groups on these alkyl radicals can be replaced by oxygen. It is advantageous for alcohols, on which the ester reagent is based, to boil at a temperature below the isononanol mixture used. A preferred reagent is dimethyl 2,5-furanedicarboxylate.

[051] Transesterification is carried out catalytically, using Br0nsted or Lewis acids or using bases, for example. Regardless of which catalyst is used, there is always a temperature-dependent balance developed between the reactants (dialkyl ester and isononanol mixture) and products (mixture of diisononyl ester and released alcohol). In order to shift the balance in favor of the diisononyl ester mixture, the resulting alcohol from the ester reagent is removed from the reaction mixture by distillation.

[052] At present, it is also useful to use the excess isononanol mixture. As transesterification catalysts, it is possible to use acids, such as sulfuric acid, methanesulfonic acid or p-toluenesulfonic acid, for example, or metals or compounds thereof. Suitable examples include tin, titanium, zirconium, which are used as finely divided metals or usefully in the form of their salts, oxides or soluble organic compounds. In contrast to protic acids, metal catalysts are high temperature catalysts that reach their full activity only at temperatures above 180 ° C. However, these are preferentially used since, in comparison with proton catalysis, they they form less by-products from the alcohol used, such as olefins, for example. Exemplary representatives of metal catalysts are tin powder, tin (II) oxide, tin (II) oxalate, titanic esters, such as tetraisopropyl orthotitanate or tetrabutyl orthotitanate, and zirconium esters, such as tetrabutyl zirconate .

[053] In addition, it is possible to use basic catalysts, such as oxides, hydroxides, hydrogen carbonates, carbonates or alkoxides of alkali metals or alkaline earth metals, for example. From this group it is preferable to use alkoxides, such as sodium methoxide, for example. Alkoxides can also be prepared in situ from an alkali metal and a nonanol and / or an isononanol mixture.

[054] The catalyst concentration is dependent on the type of catalyst. This is typically between 0.005% and 2.0% by weight, based on the reaction mixture.

[055] The reaction temperatures for transesterification are typically between 100 and 220 ° C. They should at least be high enough to allow the alcohol formed from the ester reagent to be removed by distillation at the set pressure, usually at the pressure atmospheric, from the reaction mixture.

[056] Transesterification mixtures can be purified in exactly the same way as described for esterification mixtures. USE

[057] The mixtures of isomeric nonyl esters of 2,5-furanedicarboxylic acid of the present invention can be used as plasticizers, especially in compositions of plastics, adhesives, sealants, varnishes, paints, plastisols, synthetic leathers, floor coverings, protection carcass, coated fabrics, wallpapers or paints. The plasticizers of the present invention can be used with preference in profiles, joints, food packaging, films, toys, medical articles, tiles, synthetic leathers, floor coverings, carcass protection, coated fabrics, wallpapers, cable lining and yarns, and more preferably, in food packaging, toys, medical articles, such as in bags and tube material for infusions, dialysis and drains, for example, wallpapers, floor coverings and coated fabrics.

[058] The compositions of the present invention comprising the mixture of isomeric non-esters of 2,5-furanedicarboxylic acid can be obtained using the mixture of isomeric nonyl esters of the 2,5-furanedicarboxylic acid of the present invention. .

[059] Compositions of this type may comprise the mixture of isomeric nonyl esters of the 2,5-furanedicarboxylic acid of the present invention alone or in mixtures with other plasticizers. When the compositions of the present invention comprise the mixture of isomeric nonyl esters of the 2,5-furanedicarboxylic acid of the present invention in admixture with other plasticizers, the other plasticizers can preferably be selected from the group of dialkyl phthalates, preferably , with 4 to 13 C atoms in the alkyl chain; trialkyl trimellites, preferably with 4 to 10 C atoms in the side chain; dialkyl adipates and, preferably, dialkyl terephthalates, each preferably having 4 to 13 C atoms in the side chain; 1,2-cyclohexanedicarboxylic alkyl esters, 1,3-cyclohexanedicarboxylic alkyl esters, and 1,4-cyclohexanedicarboxylic alkyl esters, preferably 1,2-cyclohexanedicarboxylic alkyl esters, each one preferably with an alkyl = alkyl radical containing 4 to 13 carbon atoms in the side chain; dibenzoic esters of glycols; alkyl sulfonic esters of phenol and, preferably, an alkyl radical containing 8 to 22 C atoms; polymer plasticizers, glycerol esters, isosorbide esters, and alkyl benzoates, preferably containing 7 to 13 C atoms in the alkyl chain. In all cases, the alkyl radicals can be linear or branched, and also identical or different. With particular preference, the composition, in addition to the mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid, comprises, in particular, an alkyl benzoate with alkyl = alkyl containing from 7 to 13 carbon atoms, preferably isononyl benzoate, nonyl benzoate, isodecyl benzoate, propyl heptyl benzoate or decyl benzoate. The fraction of mixtures of isomeric nonyl esters of the 2,5-furanedicarboxylic acid of the present invention in admixture with other plasticizers is preferably from 15% to 90% by weight, more preferably from 20% to 80% by weight , and even more preferably, from 30% to 70% by mass, with the mass fractions of all plasticizers presenting a sum to provide 100% by mass.

[060] The indicated compositions comprising mixtures of isomeric nonyl esters of 2,5-furanedicarboxylic acid and other plasticizers can be used as a plasticizer composition in compositions of plastics, adhesives, sealants, varnishes, paints, plastisols or dyes . Examples of plastic products produced from the plasticizer compositions of the present invention can include the following: profiles, joints, food packaging, films, toys, medical articles, tiles, synthetic leathers, floor covering, carcass protection, coated fabrics, wallpapers, coating of cables and wires. This group's favorites are food packaging, toys, medical articles, wallpapers, coated fabrics and floor covering.

[061] The compositions of the present invention comprising a mixture of isomeric nonyl esters of 2,5-furanedicarboxylic acid may comprise a polymer selected from polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyacrylates, preferably , polymethyl methacrylate (PMMA), polyalkyl methacrylate (PAMA), fluoropolymers, preferably polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetate, preferably polyvinylacid , polyvinyl butyral (PVB), polystyrene polymers, preferably polystyrene (PS), expandable polystyrene (EPS), acrylonitrile-styrene-acrylate (ASA), styrene-acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS), copolymer styrene-maleic anhydride (SMA), styrene-methacrylic acid copolymer, polyolefins, preferably polyethylene (PE) or polypropylene (PP), thermoplastic polyolefins (TPO), polyethylene-vinyl acetate (E VA), polycarbonates, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyamide (PA), polyethylene glycol (PEG), polyurethane (PU), thermoplastic polyurethane (TPU), polysulfides (PSU), biopolymers, preferably polylactic acid (PLA), polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV), polyesters, starch, cellulose and cellulose derivatives, preferably nitrocellulose (NC), ethyl cellulose (EC), cellulose acetate (CA), cellulose acetate / butyrate (CAB), rubber or silicones, as well as mixtures or copolymers of the indicated polymers or their monomer units. The compositions of the present invention preferably comprise PVC or homopolymers or copolymers based on ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate, methacrylates, acrylates, acrylates or methacrylates containing alkyl radicals oxygen from the ester group, from branched or unbranched alcohols containing from one to ten carbon atoms, styrene, acrylonitrile or cyclic olefins.

[062] The type of PVC in the composition of the present invention is preferably suspended PVC, bulky PVC, PVC microsuspension or PVC emulsion. Based on 100 parts by weight of polymer, the compositions of the present invention preferably comprise from 5 to 200, more preferably from 10 to 150 parts by weight of plasticizer.

[063] In addition to the indicated constituents, the compositions of the present invention may comprise additional constituents, more particularly, for example, other plasticizers, fillers, pigments, stabilizers, co-stabilizers, such as epoxidized soybean oil, for example, and also lubricating agents, fluid agents, kickers, antioxidants or biocides.

[064] The compositions of the present invention preferably take the form of a liquid, more preferably a pumpable liquid, a paste, protective compound, plastisol, powder, solid or solid.

[065] The aforementioned compositions comprising said polymers can be used as adhesives, sealants, varnishes, paints, plastisols, synthetic leathers, floor coverings, carcass protection, fabric coverings, wallpapers or dyes or for the production thereof. .

[066] When the indicated compositions comprise plastics, they can be processed into profiles, joints, one part or multiple parts closing devices, food packaging, films, toys, medical articles, particularly bag and tube material, such as used for infusions, dialysis, and drains, for example, tiles, synthetic leathers, floor covering, carcass protection, coated fabrics, wallpapers, cable and yarn coating. The compositions of the present invention are preferably used for the production of food packaging, toys, medical articles, wallpapers, and floor covering.

[067] The following examples are intended to illustrate the present invention without restricting its scope, which is evident from the description and the claims. Even without further observations, it is assumed that the person skilled in the art is capable of using the present invention in the broadest conceivable scope. EXAMPLES

[068] The esters of the present invention were prepared in a two-phase synthesis from furan-2,5-dicarboxylic acid by means of dichloride. EXAMPLE 1 SYNTHESIS PROCESS FOR -2.5- FURANODICARBONILLA DICHORIDE (II)

[069] A 250 mL three-necked flask with reflux condenser and drip funnel was charged, under argon, with 72.1 g (462 mmol) of 2,5-furanedicarboxylic acid. Over a period of 10 minutes, 165 g (1.39 mol) of thionyl chloride, to which a few drops of N, N-dimethylformamide were added, were added. The suspension was heated to reflux temperature and the resulting gas was removed by means of washing bottles containing aqueous KOH solution. The suspension was then heated for 4 hours under reflux until the evolution of the gas was complete and the dissolution of the solid was complete.

[070] After removing excess thionyl chloride, the product was isolated by distillation purification (T = 110 ° C, p = 0.0012 MPa).

[071] This provided 79.4 g of dichloride as a colorless crystalline solid (89% yield) with a melting point of 79.5 to 80.0 ° C.

[072] 2,5-Furanedicarbonyl dichloride was stored under inert gas (argon) in the dark, at room temperature, before being used later. EXAMPLE 2 SUMMARY OF 2,5-FURANODICARBOXYL ESTERS

[073] Under an argon atmosphere, a three-necked flask with reflux condenser and decanting funnel was charged with the dichloride, which was melted by heating. 2.4 equivalents of alcohol were added dropwise slowly to the liquid, and an exothermic reaction occurred with evolution of gas. The produced gas was passed through washing bottles containing aqueous KOH solution. After the complete addition, the mixture was stirred at a temperature of 80 to 100 ° C for 16 hours.

[074] The excess alcohol was removed under reduced pressure in the presence of boiling, and the crude product was purified by distillation.

[075] For the synthesis of the comparative example, commercially available 2-ethylexanol was used. To prepare the ester mixture of the present invention, the Depositor's isononanol, CAS No. 27458-94-2, commercially available under the product name of Isononanol INA, was used. The isononanol used has a density (the DIN 51757 standard) at 20 ° C of 0.8348 g / cm3, a refractive index (DIN 51423/2) at 20 ° C of 1.4362, and a shear viscosity (at DIN 53015) at 20 ° C of 13.2 mPa.s, and also a solidification point below (<) -75 ° C, and had the following composition as determined by gas chromatography analysis: 7.5% in mol of n-nonanol; 19.8 mol% of 6-methyloctanol; 20.0 mol% of 4-methyloctanol; 3.8 mol% of 2-methyloctanol; 8.3 mol% of 3-ethylene ethanol; 2.1 mol% of 2-ethylene ethanol; 1.8 mol% of 2-propylexanol; 15.0 mol% of 4,5-dimethylptanol; 10.1 mol% of 2,5-dimethylptanol; 2.5 mol% of 2,3-dimethylptanol; 4.1 mol% of 3-ethyl-4-methylexanol; 2.9 mol% of 2-ethyl-4-methylexanol; 2.1 mol% of other unidentified compounds with 9 carbon atoms; the total sum of the specified components was 100 mol%.

[076] Table 1 below records the results of the two syntheses. TABLE 1

[077] The conversions of 2,5-furanedicarbonyl dichloride (2) to the corresponding esters are therefore practically quantitative. EXAMPLE 3 DETERMINATION OF BEHAVIOR AT LOW TEMPERATURE OF ESTERS THROUGH DIFFERENTIAL SCANNING CALORIMETRY (DSC) INSTRUMENT: DSC820 FROM METTLER TOLEDO

[078] Analysis conditions: Temperature range: -100 to 250 ° C Heating rate: 10 K / minute Initial mass: about 10 - 11 mg Crucible: standard aluminum crucible with holes in the lid Gas flow: N2

[079] Result: Considering that the 2-EH ester II (Comparative Example) shows a melting signal above 0 ° C, that is, it is present in the solid form already above the freezing point, the isononyl ester I of the present The invention was subjected to vitrified solidification at about -80 ° C. In the DSC thermogram, there are no signs of apparent melting, but instead, only a glass transition point of about 80 ° C. Therefore, it can be assumed that ester I of the present invention does not become solid, even at low temperatures, but instead remains fluid and pumpable. EXAMPLE 4 PREPARATION OF PLASTISOLS

[080] The advantageous properties attainable with the esters of the present invention should be shown below in plastisols and semi-finished products capable of being obtained therefrom.

[081] The initial masses used for the components for the various plastisols are shown in Table 2 below. TABLE 2 FORMULAS [ALL VALUES IN PHR (= MASS PARTS PER 100 PVC MASS PARTS)]

[082] The liquid constituents were weighed before the solid components in a suitable PE beaker. Using a spatula, the mixture was stirred by hand so as not to leave any powder not wet. The mixture beaker was then trapped inside the fixing device of a dissolving stirrer. The sample was homogenized using a mixing disc.

[083] The rotation speed of 330 rpm was increased to 2,000 rpm, and stirring was continued until the temperature on the digital display of the thermal sensor reached 30.0 ° C. This ensured that the homogenization of the plastisol with an energy input defined. Then, the plastisol was immediately conditioned at a temperature of 25.0 ° C. EXAMPLE 5 MEASUREMENT OF THE PLASTISOL VISCOSITY

[084] The viscosities of the plastisols prepared in Example 4 were measured using a Physica MCR 101 rheometer (from Paar-Physica), controlled by the associated Rheoplus software, as follows.

[085] The plastisol was stirred again with a spatula in the stock container, and was subjected to measurement in the Z3 measuring system (DIN 25 mm), in accordance with the operating instructions. The measurement was run automatically at 25 ° C by the software mentioned above. The following procedures have been activated:

[086] A preliminary shear of 100 s-1 over a period of 60 s, during which unmeasured values were recorded (stabilization refers to thixotropic effects).

[087] A decreasing isothermal ramp, from a shear speed of 200 s-1 to 0.1 s-1, divided into a logarithmic series with 30 steps, each with a 5 s duration point measurement.

[088] The measurement data was processed automatically after the measurement by the software. The parameter produced was viscosity as a function of the shear rate. In order to capture changes in plastisol viscosity during plastisol storage (also: “plastisol aging”), measurements were taken in each case after 2 hours, 24 hours, and 7 days. Between these time points, the plastisols were stored at 25 ° C.

[089] The table below shows the corresponding viscosity values obtained after the storage times indicated in each case, for a shear rate of 100 s-1 as an example. TABLE 3 PLASTISOL VISCOSITIES AT A 100 s-1 SHEAR RATE

[090] The isononyl I esters of the present invention exhibit much smaller increases in plastisol viscosity over time compared to the 2-ethylhexyl II esters. The viscosity level of the PVC plastisol of the present invention, which is higher compared to the standard DINP plasticizer of the present formulation, can be reduced, as the skilled person knows, in (optimized) formulations and / or other compositions by through appropriate measures, such as, for example, an increase in the total amount of plasticizer, the addition of additional plasticizers with a lower intrinsic viscosity, the addition of rheological additives (eg dispersion additives or other surfactants) and / or the addition of (co) solvents. EXAMPLE 6 GELIFICATION RATE MEASUREMENT

[091] The gelation behavior of plastisols was investigated in MCR Physica 101 in oscillation mode, using a measurement plate / plate system (PP25), which was operated under the control of the shear rate. An additional temperature-conditioned hood was fitted to the instrument in order to achieve a homogeneous heat distribution and a uniform sample temperature.

[092] The set of parameters were as follows: - Mode: temperature gradient Start temperature: 25 ° C Final temperature: 180 ° C Heating / cooling rate: 5 ° C / minute Oscillation frequency: ramp 4 to 0 , 1 Hz, logarithmic Circular omega frequency: 10 1 / s Number of measuring points: 63 Duration of the measuring point: 0.5 minutes Automatic adjustment of the interval: 0 N Duration of the constant measuring point Width of the interval: 0.5 mm - Measurement procedure: A drop of the bespoke plastisol formula was applied with the spatula, without any air bubbles, on the bottom plate of the measurement system. In the course of this operation it was recalled that, after the measurement system is brought together, some plastisols may swell evenly out of the measurement system (no more than about 6 mm in all). Then, the temperature conditioning hood was positioned over the sample, and the measurement was started.

[093] The parameter determined was the complex viscosity of plastisol as a function of temperature. Because a defined temperature is reached over a period of time (determined by the heating rate of 5 ° C / min), not only the gelation temperature, but also an indication of the gelation rate of the measurement system is obtained. The beginning of the gelation process was evident from a sudden increase in the complex viscosity. The earlier the appearance of this increase in viscosity, the better the gelling capacity of the system.

[094] For comparison, the interpolation of the curves of each plastisol was used to determine the temperature at which a complex viscosity of 1000 Pa.s was reached.

[095] In this procedure, the values obtained are established in Table 4. TABLE 4 GELIFICATION BEHAVIOR

[096] Furanodicarboxylic esters clearly gel earlier (ie at lower temperatures) than the corresponding phthalates. EXAMPLE 7 MEASUREMENT OF SHORE HARDNESS OF MOLDS

[097] Shore hardness is a measure of a specimen's plasticity. The more a standardized needle can penetrate the sample within a defined measurement time, the lower the measurement value. The most efficient plasticizer provides the lowest Shore hardness value for a given amount of plasticizer. Conversely, in the case of highly efficient plasticizers, it is possible to make a certain saving in the proportion in the formula, and in many cases, this translates into lower costs for the processor.

[098] For the determination of Shore hardnesses, plastisols prepared in accordance with Example 4 were poured into circular casting molds with a diameter of 42 mm. The plastisols in the molds were then gelled in a forced air drying oven at 200 ° C for 30 minutes, demoulded after cooling, and stored at 25 ° C for at least 24 hours before measurement. The thickness of the castings was about 12 mm.

[099] The measurements were carried out in accordance with DIN 53 505 using a Zwick-Roell Shore A measuring instrument, the measurement value to be read after 3 seconds in each case. In each specimen, three different measurements were taken at different points (not in the marginal zone), and the mean was recorded in each case.

[0100] Table 5 lists the measurement values obtained. TABLE 5 SHORE A HARDNESSES

[0101] The examples listed demonstrate that the diisononyl ester of furanodicarboxylic acid I of the present invention has the decisive advantage over the closest prior art, (2-ethylexyl) -bis-furan-2,5-dicarboxylate II , of non-crystallized. Compared to the corresponding DINP phthalate, there are improvements, in some cases, significantly less, in the plasticization effect and in the gelation rate. EXAMPLE 8 USE OF THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION IN THE FORMULATION OF PVC FINISH (PLASTISOL), ALONG WITH DIISONONILLA TEREFTALATE (DINT) - PREPARATION OF PLASTISOLIS FINISHES

EXEMPLO 9 DETERMINAÇÃO DA VISCOSIDADE DO PLASTISOL DOS PLASTISSÓIS DE ACABAMENTO (DO EXEMPLO 8) QUE COMPREENDE OS ÉSTERES FURANODICARBOXÍLICO DA PRESENTE INVENÇÃO E O TEREFTALATO DE DIISONONILA APÓS UM PERÍODO DE ARMAZENAMENTO DE 24 H (A 25° C)[0102] Plastisols were prepared according to Example 4, but with a modified formula. The initial masses used for the components of the various plastisols are shown in the table below (Table 6). TABLE 6 FORMULAS [All figures in phr (= parts by mass per 100 parts by mass of PVC)]

EXAMPLE 9 DETERMINATION OF THE PLASTISOL VISCOSITY OF THE FINISHING PLASTISOLS (FROM EXAMPLE 8) THAT UNDERSTANDS THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION AND THE DIISONONILLA TEREFTALATE AFTER A 24-HOUR STORAGE PERIOD (25 H) OF STORAGE

[0103] The viscosities of the plastisols prepared in Example 8 were measured using a Physica MCR 101 rheometer (from Paar-Physica), according to the procedure described in Example 5. The results are shown in the table below (Table 7) by means of example for shear rates of 100 / s, 10 / s, 1 / s and 0.1 / s. TABLE 7 SHEARING VISCOSITY OF PLASTISOLS IN EXAMPLE 8, AFTER 24 H OF STORAGE AT 25 ° C

[0104] In a range of low shear rates, the plastisols comprising the furanodicarboxylic esters of the present invention are in terms of their shear viscosity at or below the level of the plastisol DINP analog. At higher shear rates, the shear viscosities of the plastisols of the present invention are only slightly above the shear viscosity of the plastisol analog DINP. By mixing the diisononyl terephthalate with the furanodicarboxylic esters of the present invention, therefore, it is possible to prepare plastisols which have similar processing properties to DINP plastisols, but at the same time do not contain orthophthalates, and which are based on renewable raw materials . EXAMPLE 10 USE OF THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION IN THERMALLY EXPANDABLE PLASTISOLS (COATING), ALONG WITH QUICK GELIFICANTS - PREPARATION OF PLASTISOLS

[0105] Plastisols were prepared as in Example 4, but with a modified formula. The initial masses used in the components for the various plastisols are shown in the table below (Table 8). TABLE 8 THERMALLY EXPANDABLE PLASTISOL FORMULAS [All figures in phr (= parts by mass per 100 parts by mass of PVC)]

[0106] The compounds and substances used are explained below: Vinnolit MP 6852: Microsuspensions of PVC (homopolymer) with K value (according to DIN EN ISO 1628-2) of 68, from Vinnolit GmbH & Co KG. Vestinol 9: (ortho) diisononyl phthalate [DINP], plasticizer; from Evonik Oxeno GmbH. Citrofol BII: fast-curing plasticizer, acetyl tributyl citrate, from Jungbunzlauer AG. Mesamol II: phenol alkyl sulfonic ester; plasticizer with rapid coagulation; from Lanxess AG. Jayflex MB10: isodecyl benzoate; fast coagulation plasticizer from ExxonMobil Chemicals. Eastman DBT: dibutyl terephthalate; fast coagulating plasticizer, from Eastman Chemical Co. DINFDC: diisononyl 2,5-furanedicarboxylate of the present invention; preparation as in Example 2. Unifoam AZ Ultra 7043: Azodicarbonamide; thermally activated blowing agent, from Hebron S.A. ZnO: zinc oxide; decomposition catalyst for the thermal blowing agent; reduces the blowing agent's inherent decomposition temperature; active zinc oxide; from Lanxess AG. EXAMPLE 11 DETERMINATION OF THE VISCOSITY OF THERMALLY EXPANDABLE PLASTISOLS (FROM EXAMPLE 10) UNDERSTANDING THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION AND (ORTO) DYLISONONILLA PHYTALATE AND / OR GELIFANTS RAPID OF THE PERIOD OF ATTENTION OF ATTENTION TO (A) 24 HOURS OF RAPID AFTER 25 HOURS (A) AT THE TIME

[0107] The viscosities of the plastisols prepared in Example 10 were measured using a Physica MCR 101 rheometer (from Paar-Physica), in accordance with the procedure described in Example 5. The results are shown in the table below (Table 9) by means of example for shear rates of 100 / s, 10 / s, 1 / s, and 0.1 / s. TABLE 9 SHEARING VISCOSITY OF PLASTISOLS IN EXAMPLE 8, AFTER 24 H OF STORAGE AT 25 ° C

[0108] By choosing the quick gelling agent, it is possible to adjust the viscosity of plastisol in a deliberate way, with the combination of diisononyl furanedicarboxylate of the present invention and alkyl benzoate, in the present case (Formula 5 plastisol) leading to a behavior similar to that found when using the universal plasticizer (ortho) diisononyl phthalate. In other words, the plastisols of the present invention are provided, which can be used under similar processing conditions (for example, application rates) as the current standard DINP plasticizer, but do not (have to) contain orthophthalates and are based, at least partly in renewable raw materials. EXAMPLE 12 PRODUCTION OF FOAM SHEETS AND DETERMINATION OF THE EXPANSION BEHAVIOR AND FOAM FORMATION OF THE THERMALLY EXPANDABLE PLASTISOLS (FROM EXAMPLE 10) THAT UNDERSTAND THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION AND (ORTHONY) RIDONIDOS ORIDONIS ORYLIDON RYALIDATE (R)

[0109] The foaming behavior was determined using a quick thickness gauge (suitable for plasticized PVC measurements) to an accuracy of 0.01 mm. For sheet production, a 1 mm blade opening was defined on the blade roll of a Labcoaters Mathis (manufacturer: W. Mathis AG). This opening of the slide was checked with a calibrator and adjusted, if necessary. The plastisols prepared in Example 10 were coated using the Labcoater Mathis rolling blade on a release paper (GUARANTEES Paper Release; from Sappi Ltd) stretched flat on a board. In order to be able to calculate the percentage of foaming, an incipiently gelled and foamless sheet was first produced. The thickness of this sheet with the indicated blade opening was 0.74 mm. The thickness was measured at three different points on the sheet. Subsequently, again with / in the Labcoater Mathis, the foam sheets (foams) were produced with four different residence times in the oven (60, 90, 120s and 150s). After the foams had cooled, the thickness was also measured at three different points. The average values of the thicknesses, and the original thickness of 0.74 mm, were necessary for the calculation of the expansion (example: (foam thickness - original thickness) / original thickness * 100% = expansion). The results are shown in the table below (Table 10). TABLE 10 EXPANSION FEES OF POLYMER FOAMS PREPARED FROM THERMAL EXPANDABLE PLASTISOLS (FROM EXAMPLE 10) WITH DIFFERENT RESIDENCE TIMES IN THE OVEN AT LABCOATER MATHIS AT 200 ° C

[0110] The plastisol formulas of the present invention which comprise diisononyl furanodicarboxylates expand much faster than with the diisononyl phthalate plasticizer used alone in the comparative example (Formula 1 plastisol). Through the deliberate use of specific fast gelling agents, such as certain citric acid esters, for example (Formula 3 plastisol), PVC plastisols can be prepared which, on the one hand, can be subjected to heat pretreatment (for example, example, preliminary gelling in the case of a multilayered construction), without exhibiting measurable expansion at this initial point, but on the other hand, they expand later even more quickly. Through the selection of different plasticizer combination partners, it is also possible to prepare PVC plastisols which (such as plastisol of Formulas 4 and 5, for example) exhibit strong expansion right from the start, and allow for significantly less total processing time compared to the current standard DINP plasticizer. PVC plastisols are therefore supplied, which have a wide spectrum of different processing possibilities. EXAMPLE 13 DETERMINATION OF THE THERMALLY EXPANDABLE PLASTISOL GELIFICATION BEHAVIOR (FROM EXAMPLE 10) THAT UNDERSTANDS THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION AND DIISONONILLA (/ ORTH) PHALATE AND / OR FAST GELIFICANTS

[0111] The gelation behavior of the thermally expandable plastisols prepared in Example 10 was investigated in the MCR Physica 101 in oscillation mode using a plate / measurement plate system (PP25) which was operated under shear rate control, in accordance with with the procedure described in example 6. The determined parameter was the complex viscosity of plastisol as a function of temperature, with a constant heating rate (ie, the gelation curve). The start of the gelation process results from a sudden increase in the complex viscosity. The sooner this increase in viscosity appears, the faster the corresponding plastisol will gel. By interpolating each plastisol, the measurement curves obtained were used to determine the temperatures at which a complex viscosity of 1000 Pa.se and 10 000 Pa.s was reached. In addition, a tangent method was used to determine the maximum plastisol viscosity achieved in the present experimental system, and the temperature from which the maximum plastisol viscosity occurs was determined by the drop of a perpendicular. The results are shown in the table below (Table 11). TABLE 11 KEY DATA, DETERMINED FROM THE GELIFICATION CURVES (VISCOSITY CURVES), THE GELIFICATION BEHAVIOR OF THE THERMALLY EXPANDABLE PLASTISOLS PREPARED IN EXAMPLE 10

[0112] By choosing the quick gelling agent, it is not only possible, but expected, to adjust the gelling rate and also the gelling temperature, but also, to a surprisingly high degree, the maximum viscosity of the fully gelled plastisol (maximum plastisol viscosity ), and therefore the physical properties of PVC foam produced through thermal expansion. Therefore, thermally expandable PVC plastisols are supplied, which on the one hand gels substantially faster than plastisols produced using the current DINP plasticizer alone, but on the other hand can also be processed into foams with significantly higher viscosity, and greater strength and / or elasticity. EXAMPLE 14 USE OF THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION IN CONJUNCTION WITH OTHER DRY MIXTURES PLASTIFIERS - DRY MIXTURES PRODUCTION

[0113] The advantageous properties obtained with the esters of the present invention will be demonstrated below as an example for dry mixtures, known as dry mixtures, and for semi-finished products that can be obtained from these mixtures. The prepared formulas are shown in the table below (Table 12). TABLE 12 DRY MIXTURES FORMULAS [All figures in phr (= parts by mass per 100 parts by mass of PVC)]

[0114] The compounds and substances used are explained below: Solvin S 271 PC: PVC suspension with a K value (determined to DIN EN ISO 1628-2) of 71, by SolVin, SA Vestinol 9: (ortho) phthalate diisononyl [DINP], plasticizer; from Evonik Oxeno GmbH. DEHT: di (2-ethylhexyl) terephthalate; "Eastman 168"; plasticizer from Eastman Chemical. DINT: diisononyl terephthalate (laboratory product, prepared according to document DE 102008006400 A1 / Example 1). DINCH: Di (isononyl) cyclohexanedicarboxylate; DINCH hexamoll; plasticizer; BASF AG. GSS: 12- (acetyloxy) -2,3-bis (acetyloxy) propyl ester; glycerol triester produced from castor oil; “Soft Grindsted 'n Safe”; plasticizer; from Danisco A / S. Polysorb ID 37: Di (octanoic acid) ester isosorbide; plasticizer; from Roquette Freres. DINFDC: diisononyl 2,5-furanedicarboxylate of the present invention; preparation as in Example 2. Drapex 39: epoxylated soybean oil; Costabilizer &Coplasticizer; from Chemtura / Galata. Mark BZ 561: barium / zinc stabilizer, from Chemtura / Galata. Calcium stearate: Calcium salt of stearic acid; lubricant.

[0115] The dry mixes were produced in a Brabender planetary mixer. A thermostat heated the mixing bowl of the planetary mixer to a constant temperature of 90 ° C. Using the “Winmix” software, the following parameters were defined in the Brabender planetary mixer: Rotation speed program: Active Profile: Rotation speed of 50 rpm, wait time: 9 min, increase time: 1 min Rotation speed at 100 rpm; Waiting time: 20 min Kneader temperature: 88 ° C Measuring range: 2 Nm Attenuation: 3

[0116] The temperature in the mixing vessel was 88 ° C. After the planetary mixer performed the self-calibration, solid constituents were supplied to the mixing vessel. The program was started and the powder mixture was stirred in the mixing vessel for 10 minutes and brought to a controlled temperature before the liquid constituents were added. The mixture was stirred in the planetary mixer for another 20 minutes. After the end of the program, the completed dry mixture (powder) was discharged. The transferred torque / time diagram was evaluated by the Brabender software. After the addition of the liquid constituents, a distinct increase is evident in the curve. Only when the curve falls significantly again, the incorporation of the plasticizer is completed. The difference in time between these two points is the time of incorporation of the plasticizer (dry mix time). The maximum torque is automatically evaluated by the program. The incorporation of the plasticizer and the maximum torque determined in the production of the dry mixtures are shown in Table 13. TABLE 13 TIME NECESSARY FOR THE INCORPORATION OF THE LIQUID COMPONENTS OF THE FORMULA BY THE PRE-HEATED PVC (INCORPORATION OF THE PLASTICANT) AND THE MAXIMUM TORQUE DETERMINED DURING PRODUCTION DRY MIXTURE

[0117] The processing speed of the mixtures of the present invention is higher, in some cases much less, than for the comparative formula with the standard DINP plasticizer; the maximum torque is comparable in all cases. Therefore, dry mixtures are provided which, compared to the current standard DINP plasticizer, allow a significantly higher processing rate for a similar applied force. EXAMPLE 15 PRODUCTION OF MILLED SHEETS AND MOLDED PLATES IN PRESS FROM DRY MIXTURES (FROM EXAMPLE 14) UNDERSTANDING THE HYDRO-CARBOXYLIC ESTERS OF THIS INVENTION IN conjunction with OTHER PLASTICING MILLS OF MILLED SHEETS

[0118] The milled sheets were produced in a Collin AP W150 calender.

[0119] The parameters established in the calender were as follows: Roll temperature: 165 ° C Roll gap: 0.5 mm Rolling time: 5 minutes Five-phase program for the production of the milled sheet

[0120] When the roll temperature has been reached, the roll slot has been calibrated. At the beginning of the measurement, the roll slot was adjusted to 0.2 mm. 160 grams of a dry mixture (from Example 14) were weighed in each case and placed in the roll slot, with the rollers stationary. The program has started. The rollers started with a rotation speed of 5 rpm and a friction of 20%. After about 1 minute, plasticization was largely at the end, and the roll slot was enlarged to 0.5 mm. Triple homogenization was performed by means of an automatic volume unit in the calender. After 5 minutes, the milled sheet was removed from the roll and cooled. PRODUCTION OF PRESS MOLDED PLATES

[0121] Press-molded plates were produced in a Collin laboratory press. The prefabricated milled sheets (see above) were used to produce the press-molded plates. The lateral margins of the milled sheets were removed by means of a shearing machine, after which the milled sheet was cut into sections measuring approximately 14.5 x 14.5 cm. For the 1 mm thick molded plates, two sections of milled sheets were placed in 15 x 15 cm stainless steel pressing frame.

[0122] The parameters established in the laboratory press were as follows: Three-phase program: Phase 1: Both plates at 165 °; plate pressure in the press: 5 bar, phase time: 60 seconds. Phase 2: Both plates at 165 °; plate pressure in the press: 200 bar; phase time: 120 seconds. Phase 3: Both plates at 40 °; plate pressure in the press: 200 bar, phase time: 270 seconds.

[0123] The excess press exudate was removed after the molded plates on the press were produced. EXAMPLE 16 DETERMINATION OF THE PLASTIFICATION EFFECT AND PLASTICING EFFICIENCY ON PRESS MOLDED PLATES PRODUCED FROM THE DRY MIXTURES UNDERSTANDING THE FURANODICARBOXYLIC ESTERS OF THIS INVENTION IN CONNECTION WITH OTHER PLASTIFIERS (DETERMINATION)

[0124] Shore hardness is a measure of the plasticity of a specimen. The more a standardized needle can penetrate the sample within a defined measurement time, the lower the measurement value. For a given amount of plasticizer, the plasticizer with the highest efficiency produces the lowest value for Shore hardness. Since, in practice, formulations / formulas are often defined or optimized for a defined Shore hardness, accordingly, it is possible in the case of very efficient plasticizers to save on the formula of a given fraction, which implies a reduction in costs for the processor.

[0125] Hardness measurements were performed in accordance with DIN 53 505 using a Shore A and Shore D Zwick-Roell measuring instrument, the measurement value to be read after 3 seconds in each case. On each specimen (produced as in Example 15), measurements were taken at three different points, and an average was formed. The results of the hardness determination are summarized in table 14. TABLE 14 SHORE A AND SHORE D HARDNESSES OF PRESS MOLDED PLATES PRODUCED (ACCORDING TO EXAMPLE 15) FROM THE DRY MIXTURES (FROM EXAMPLE 14) UNDERSTANDING THE INVENTORY FURANODICBOXYLIC ESTERS IN conjunction with other plasticizers

[0126] Mixing different standard plasticizers with the furanodicarboxylic esters of the present invention in dry mixtures produces a plasticizer efficiency that is similar to or better than that of DINP (plasticizer standard). In addition, dry mixtures are provided which, compared to DINP presently in use as a universal plasticizer, exhibit significantly better efficiency and, therefore, can lead to, in particular, reduced formula costs. EXAMPLE 17 DETERMINATION OF WATER ABSORPTION AND LIXIVATION BEHAVIOR IN MOLDED PRESS PLATES (SEMI-FINISHED PRODUCTS) PRODUCED FROM DRY MIXTURES UNDERSTANDING THE FURANODICBOXYL ESTERS OF THIS INVENTION IN CONNECTION WITH OTHERS

[0127] Water absorption and leaching behavior are two main criteria for assessing the quality of semi-finished products produced based on dry PVC mixtures. If a semi-finished PVC product absorbs water to a substantial extent, this results, on the one hand, in a change in its physical properties, and on the other hand, in a change in its visual appearance (for example, cloudy). A high level of water absorption, accordingly, is generally undesirable. The leaching behavior is an additional criterion of the permanence of the components of the formulation under conditions of use (for example, on floors or tiles). This applies particularly to stabilizers, plasticizers and / or their ingredients, since a reduction in the concentration of these constituents in the formula of the semi-finished product can not only impair the physical properties, but also drastically reduce the life span of the semi-finished products. PRODUCTION OF TEST SPECIMENS

[0128] For each sample / dry mix, 3 circles (each 10 cm2) were cut with the aid of a circular cutter from the plates molded in a press (produced as in Example 15). The circles were punctured. Before storing the water, the circles were stored in a desiccator equipped with drying agent (KC drying beads) at 25 ° C for 24 hours. The original weight (starting mass) was determined on an analytical balance to an accuracy of 0.1 mg. The circles were then stored in a shaking bath filled with completely demineralized water, at a temperature of 30 ° C, below the water surface, with suitable sample holders, for 24 hours, and were moved continuously. After storage, the circles were removed from the water bath, dried and weighed (weight after 24 h). The heavy circles were placed back in the water bath and after 7 days, weighed again in the dry state (weight after 7 days). After the second weighing, the cycles were again stored in a desiccator equipped with drying agent (KC drying beads) at 25 ° C for 24 hours, and then weighed again (final mass = weight after drying). The changes in weight were calculated as percentages and are shown in Table 15. TABLE 15 WATER ABSORPTION AND LEACHING BEHAVIOR DETERMINED IN TEST SPECIMENS PRODUCED FROM PRESS MOLDED PLATES (AS IN EXAMPLE 15) PRODUCED FROM DRY MIXTURES ( FROM EXAMPLE 14) UNDERSTANDING THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION IN CONNECTION WITH OTHER PLASTIFIERS

[0129] Test specimens comprising furanodicarboxylic esters are similar in terms of water storage behavior in the test specimen containing only the standard plasticizer DINP. Water absorption is extremely low, which is a special advantage for calendered floor coverings, but also for roofing sheets. Mass loss through leaching is also within narrow limits, with the exception of the mixture of isosorbide ester Polysorb ID 37 and diisononyl furanedicarboxylate. Thus, dry mixes and semi-finished products with a production capacity from them are supplied, which are distinguished by low water absorption and low leaching characteristics, and are therefore ideal also for use in contact areas. with continuous or frequent water. EXAMPLE 18 DETERMINATION OF TENSION / STRETCH PROPERTIES IN PRESS MOLDED PLATES (SEMI-FINISHED PRODUCTS) PRODUCED FROM DRY MIXTURES UNDERSTANDING THE FURANODICBOXYLIC ESTERS OF THIS INVENTION IN CONJUNCTION WITH OTHER PLASTICING PLANTS

[0130] Tensile strength and elongation at break are physical properties that play an important role, especially for semi-finished products under mechanical load. This mechanical load can occur both during the production process of the semi-finished product and during its use. Preferably (particularly in the tile sector) materials that exhibit high tensile strength with moderate elongation are given in most cases.

[0131] For the tensile tests, standard “S-2” test bars were perforated from the press molded sheets produced as in Example 15. The tensile tests were carried out in accordance with DIN 53504 on a tensile tester Zwick “Z 1445” traction.

[0132] The set of test parameters were as follows: Test conditions: 23 ° C, RH 50% Initial force: 0.5 N Initial force speed: 5 mm / minute Test speed: 100 mm / minute

[0133] To determine the tensile strength and elongation at break, 5 measurements were taken per sample. The average measurement values were inserted in the table below (Table 16). TABLE 16 TRACTION PROPERTIES DETERMINED ACCORDING TO DIN 53504 IN S2 TEST SAMPLES PRODUCED FROM PRESS MOLDED PLATES (AS EXAMPLE 15) PRODUCED FROM DRY MIXTURES (FROM EXAMPLE 14) UNDERSTANDING THE HYDROGRAPHY OF THE HYDROGRAPHY OF THE HYDROGENIC PROTEIN. WITH OTHER PLASTIFIERS

[0134] By using the mixtures of the present invention it is possible to achieve a considerable increase in tensile strength, compared to pure DINP (plasticizer standard). There are no restrictions at present on the flexibility of the material, instead, the elongation at break is in fact somewhat increased. Therefore, dry mixtures and semi-finished products with production capacity from them are supplied, which are distinguished by high tensile strength together with high flexibility and high dimensional stability, and which are therefore also suitable for use under high mechanical load (for shoring, among other uses). EXAMPLE 19 USE OF THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION IN PROTECTIVE COMPOUNDS (EXAMPLE, BOTTOM OF THE PROTECTIVE BODY / UBP) - PREPARATION OF UBP PLASTISOLS)

EXEMPLO 20 DETERMINAÇÃO DA VISCOSIDADE DO PLASTISOL DOS PLASTISSÓIS UBP COMPREENDENDO OS ÉSTERES FURANODICARBOXÍLICO DA PRESENTE INVENÇÃO, APÓS UM TEMPO DE ARMAZENAMENTO DE 2 H (A 25° C)[0135] The advantageous properties attainable with the esters of the present invention will be demonstrated below in the UBP plastisols (protective compounds). Plastisols were prepared as in Example 4, but with a modified formula. The initial masses used for the components of the various plastisols can be seen from the table below (Table 17). TABLE 17 UBP PROTECTIVE COMPOUND FORMULAS (PLASTISOLS) [All figures in phr (= parts by mass per 100 parts by mass of PVC)]

EXAMPLE 20 DETERMINATION OF PLASTISOL VISCOSITY OF UBP PLASTISOLS UNDERSTANDING THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION AFTER A 2 H STORAGE TIME (AT 25 ° C)

[0136] Protective compounds, especially those used in the vehicle body protection area, are required to meet different viscosity requirements according to the current shear rate. Therefore, during application, which is generally carried out at high spray shear rates, the protective compounds must flow very easily and exhibit, on the treated surface, a homogeneous spray pattern and good leveling. After application (that is, in the absence, to a large extent, of any shear force), in contrast, they must have a high viscosity and to exhibit little post-application flow.

[0137] The viscosities of the plastisols prepared in Example 19 were measured using a Physica MCR 101 rheometer (from Paar-Physica), according to the procedure described in Example 5, after the pastes had been conditioned at temperature for a period of 2 hours at 25 ° C. The results are shown in the table below (Table 18) by way of example for shear rates of 100 / s, 10 / s, 1 / s, and 0.1 / s. TABLE 18 SHEARING VISCOSITY OF PLASTISOLS IN EXAMPLE 19, AFTER 2 HOURS OF STORAGE AT 25 ° C

[0138] Compared to DINP (plasticizer standard, Formula 2 plastisol), the UBP / plastisol UBP paste based on the furanodicarboxylic ester mixture of the present invention (Formula 1 plastisol) also has a low shear viscosity with high rates of shear, while at low shear rates it is well above the shear viscosity of the DINP paste. Therefore, in the application with the same processing properties, there is a clear advantage in terms of the drip resistance of the formulation. Thus, UBP plastisols are provided that combine excellent spraying and leveling with very low post-application flow properties. EXAMPLE 21 DETERMINATION OF THE UBP PLASTISOL GELIFICATION RATE UNDERSTANDING THE FURANODICARBOXYL ESTERS OF THE PRESENT INVENTION

[0139] The gelation of UBP protective compounds must be possible, within the framework of thermal curing processes that exist in the automotive industry. On the one hand, an important factor is an extremely rapid solidification of the protective compound, in order to prevent further dripping, while, on the other hand, another important factor is a complete or almost complete gelation within an extremely short time, the in order to achieve maximum protection effect.

[0140] The gelation behavior of the UBP plastisols prepared in Example 19 was investigated in Physica MCR 101 in oscillation mode using a measurement plate / plate system (PP25) which was operated under the control of the shear rate, according to with the procedure described in Example 6.

[0141] The determined parameter was the complex viscosity of plastisol as a function of temperature, with a constant heating rate (ie, the gelation curve). The start of the gelation process results from a sudden increase in the complex viscosity. The sooner this increase in viscosity appears, the faster the corresponding plastisol will gel. By interpolation for each plastisol, the measurement curves obtained were used to determine the temperatures at which the viscosity of a 1,000 Pa.se and 10,000 Pa.s complex was reached. In addition, a tangent method was used to determine the maximum plastisol viscosity achieved in the present experimental system, and the temperature from which the maximum plastisol viscosity occurs was determined by the drop of a perpendicular. The results are shown in the table below (Table 19). TABLE 19 KEY DATA, DETERMINED FROM THE GELIFICATION CURVES (VISCOSITY CURVES), THE GELIFICATION BEHAVIOR OF THE UBP PLASTISOLS PREPARED IN EXAMPLE 19

[0142] The UBP protective compound comprising the furanodicarboxylic esters of the present invention exhibits a substantially faster gelation than the comparable DINP protective compound; consequently, substantially faster processing or, alternatively, the use of lower processing temperatures (= energy and cost savings) is possible. The substantially higher final viscosity of the UBP protective compound of the present invention also points to an improved effect of protecting the compound against stone scratches, for example. Therefore, UBP plastisols are provided, which compared to UBP plastisols based on the present standard DINP plasticizer, have significantly better processing and physical properties. EXAMPLE 22 EFFECT OF ADHESION OF UBP PROTECTIVE COMPOUNDS UNDERSTANDING THE FURANODIC CARBOXYL ESTERS OF THE PRESENT INVENTION ON STANDARD METAL PANELS

[0143] Crucial to the ongoing protective effect of UBP protective compounds are, among other properties, the adhesion properties of fully gelled UBP protective compounds on automotive body panels.

[0144] For the adhesion test, specially coated “Cathogard” panels (BASF Coatings GmbH) were used. A metering slide was used to coat the metal panels with the UBP plastisols of Example 19. The UBP plastisols were used after a storage time of 2 hours at 25 ° C. For the coating, the metal panels were labeled with adhesive tape , in order to produce four areas with a size of about 7 x 3 cm. Plastisols were first distributed over the four areas using a spatula. With the metering blade, the plastisols were then coated without problems. Excess plastisol and adhesive tape have been removed. The coated panels were gelled in a drying oven at a temperature of 130 ° C for 25 minutes.

[0145] The adhesion test was carried out after three different time conditions (2 hours / 24 hours / 168 hours). For the test, the areas were divided with a razor blade for a number of small areas. Then, using a special-purpose spatula, an attempt was made to separate the first area. The adhesion / detachment behavior was assessed (see Table 20). Between tests, the fully gelled panels were stored in a temperature conditioning cabinet at 25 ° C. TABLE 20 ASSESSMENT SYSTEM FOR THE ADHESION / REMOVAL TEST ON THE FULLY GELIFIED PLASTISOLS UBP

[0146] The results of the adhesion / detachment test on the fully gelled UBP plastisols are collected in the table below (Table 21). TABLE 21 ADHESION / REMOVAL PROPERTIES OF TOTALLY GELED UBP PLASTISOLS, PREPARED ACCORDING TO EXAMPLE 19

[0147] The protective compound comprising the furanodicarboxylic esters of the present invention therefore has the same adhesion properties as the analogous protective compound DINP. Thus, the UBP protection compounds that are provided, which in addition to very good processing and physical properties also have a good adhesion to car panels and, therefore, have a good protective effect.

Claims (15)

1. ISOMERIC NONYL ESTER MIXTURES, characterized by being mixtures of isomeric nonyl esters of Formula I-2,5-furanedicarboxylic acid:

2. MIXTURES according to claim 1, characterized in that they comprise at least two different esters, which differ in the constitution of the isomeric C9 radicals, with none of the C9 radicals present in the mixture with a fraction greater than 90 mol%. 3. PROCESS FOR THE PREPARATION OF ISOMERIC NONILLA ESTER MIXTURES, of Formula I-2,5-furanedicarboxylic acid, as defined in claim 1, characterized by: (a) 2,5-furanedicarboxylic acid being brought into contact with a mixture of isomeric C9 alcohols, with water release; (b) the mixture of isomeric C9 alcohols is used in a molar excess of up to 50%; (c) the reaction in (a) occurs using a catalyst selected from the groups of Br0nsted acids and / or Lewis acids. 4. PROCESS FOR THE PREPARATION OF ISOMERIC NONILLA ESTER MIXTURES, of the 2,5-furanedicarboxylic acid of Formula I, as defined in claim 1, characterized in that: (a) the 2,5-furanedicarboxylic acid is converted into the corresponding chloride of -2,5-furanodicarbonyl, which (b) following isolation and purification, is subsequently brought into contact with a mixture of isomeric C9 alcohols, with the release of hydrogen chloride. 5. PROCESS FOR THE PREPARATION OF ISOMERIC NONILLA ESTER MIXTURES, of the formula I 2,5-furanedicarboxylic acid, as defined in claim 1, characterized in that: (a) the dimethyl 2,5-furanedicarboxylate is placed in contact with a mixture of isomeric C9 alcohols, with methanol release; (b) the reaction in (a) occurs using a catalyst selected from the groups of Br0nsted acids and / or Lewis acids. 6. COMPOSITION, characterized by comprising mixtures of isomeric nonyl esters of the 2,5-furanedicarboxylic acid of Formula I, as defined in claim 1, and also plasticizers selected from the group of alkyl benzoates, dialkyl adipates, glycerol esters, citric acid trialkyl esters, citric acid acylated trialkyl esters, trialkyl trimellites, glycol dibenzoates, dialkyl terephthalates, dialkyl phthalates, isosorbide dialkoyl esters and / or the dialkyl esters of 1,2-, 1 , 3- or 1,4-cyclohexanedicarboxylic. 7. COMPOSITION, according to claim 6, characterized by the ratio between the isomeric nonyl esters of the 2,5-furanedicarboxylic acid of Formula I and the plasticizers being in the range of 1:15 to 15:01. COMPOSITION according to claim 7, characterized in that it comprises a polymer selected from polyvinyl chloride, polyvinyl butyral, polylactic acid, polyhydroxybutyral and / or polyalkyl methacrylate. 9. COMPOSITION, characterized by comprising mixtures of isomeric nonyl esters of the 2,5-furanedicarboxylic acid of Formula I, as defined in claim 1, and a polymer selected from polyvinyl chloride, polyvinyl butyral, polylactic, polyhydroxy butyric acid and / or polyalkyl methacrylate. 10. COMPOSITION according to claim 9, characterized in that the ratio of polymer and isomeric nonyl esters of 2,5-furanedicarboxylic acid of Formula I is in the range of 30: 1 to 1: 2.5. 11. USE OF ISOMERIC NONILA ESTERS, of Formula I-2,5-furanedicarboxylic acid, as defined in any one of claims 1 to 2, characterized as being plasticizers. 12. USE OF THE COMPOSITION, as defined in any one of claims 6 to 9, characterized in that it is in the preparation of paints, dyes, adhesives or adhesive components, varnishes, plastisols, sealants as plasticizers, more particularly in plastics or plastic components. 13. USE OF THE COMPOSITION, as defined in any of claims 6 to 9, characterized as being a solvent in the preparation of paints, dyes, adhesives or adhesive components, varnishes, plastisols, sealants. 14. USE OF THE COMPOSITION, as defined in any one of claims 6 to 9, characterized as being a component of lubricating oil. 15. USE OF THE COMPOSITION, as defined in one of claims 6 to 9, characterized as being an aid in the processing of metals.